EP0379515A1 - Low pressure rhodium catalyzed hydroformylation of olefins. - Google Patents
Low pressure rhodium catalyzed hydroformylation of olefins.Info
- Publication number
- EP0379515A1 EP0379515A1 EP88908046A EP88908046A EP0379515A1 EP 0379515 A1 EP0379515 A1 EP 0379515A1 EP 88908046 A EP88908046 A EP 88908046A EP 88908046 A EP88908046 A EP 88908046A EP 0379515 A1 EP0379515 A1 EP 0379515A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphine
- range
- accordance
- tris
- rhodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010948 rhodium Substances 0.000 title claims abstract description 62
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 61
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 28
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- -1 C20 mono-olefins Chemical class 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001241 acetals Chemical class 0.000 claims description 6
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- DENLPXAPHRQMRW-UHFFFAOYSA-N tris[(2-fluorophenyl)methyl]phosphane Chemical compound FC1=CC=CC=C1CP(CC=1C(=CC=CC=1)F)CC1=CC=CC=C1F DENLPXAPHRQMRW-UHFFFAOYSA-N 0.000 claims description 2
- FQZJSTBXYQALIN-UHFFFAOYSA-N tris[(3,4-dichlorophenyl)methyl]phosphane Chemical compound C1=C(Cl)C(Cl)=CC=C1CP(CC=1C=C(Cl)C(Cl)=CC=1)CC1=CC=C(Cl)C(Cl)=C1 FQZJSTBXYQALIN-UHFFFAOYSA-N 0.000 claims description 2
- QOQINGLMKGDYJA-UHFFFAOYSA-N tris[(3,5-dimethylphenyl)methyl]phosphane Chemical compound CC1=CC(C)=CC(CP(CC=2C=C(C)C=C(C)C=2)CC=2C=C(C)C=C(C)C=2)=C1 QOQINGLMKGDYJA-UHFFFAOYSA-N 0.000 claims description 2
- XGDSDEHIRGOWGK-UHFFFAOYSA-N tris[(3-chlorophenyl)methyl]phosphane Chemical compound ClC1=CC=CC(CP(CC=2C=C(Cl)C=CC=2)CC=2C=C(Cl)C=CC=2)=C1 XGDSDEHIRGOWGK-UHFFFAOYSA-N 0.000 claims description 2
- OXDHSVIGJNGMRC-UHFFFAOYSA-N tris[(3-fluorophenyl)methyl]phosphane Chemical compound FC1=CC=CC(CP(CC=2C=C(F)C=CC=2)CC=2C=C(F)C=CC=2)=C1 OXDHSVIGJNGMRC-UHFFFAOYSA-N 0.000 claims description 2
- GLUMUYNXDBSCTI-UHFFFAOYSA-N tris[(4-chlorophenyl)methyl]phosphane Chemical compound C1=CC(Cl)=CC=C1CP(CC=1C=CC(Cl)=CC=1)CC1=CC=C(Cl)C=C1 GLUMUYNXDBSCTI-UHFFFAOYSA-N 0.000 claims description 2
- GGAUWSLWHFBDSK-UHFFFAOYSA-N tris[(4-fluorophenyl)methyl]phosphane Chemical compound C1=CC(F)=CC=C1CP(CC=1C=CC(F)=CC=1)CC1=CC=C(F)C=C1 GGAUWSLWHFBDSK-UHFFFAOYSA-N 0.000 claims description 2
- JYMHPKNCPVYQRK-UHFFFAOYSA-N tris[(4-tert-butylphenyl)methyl]phosphane Chemical compound C1=CC(C(C)(C)C)=CC=C1CP(CC=1C=CC(=CC=1)C(C)(C)C)CC1=CC=C(C(C)(C)C)C=C1 JYMHPKNCPVYQRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- BPPREZOFWLOXDA-UHFFFAOYSA-N tris[(2-methylphenyl)methyl]phosphane Chemical compound CC1=CC=CC=C1CP(CC=1C(=CC=CC=1)C)CC1=CC=CC=C1C BPPREZOFWLOXDA-UHFFFAOYSA-N 0.000 claims 1
- RAVACSWYIIPFFV-UHFFFAOYSA-N tris[(4-methoxyphenyl)methyl]phosphane Chemical compound C1=CC(OC)=CC=C1CP(CC=1C=CC(OC)=CC=1)CC1=CC=C(OC)C=C1 RAVACSWYIIPFFV-UHFFFAOYSA-N 0.000 claims 1
- YFJBZOCDTYZZBH-UHFFFAOYSA-N tris[(4-methylphenyl)methyl]phosphane Chemical compound C1=CC(C)=CC=C1CP(CC=1C=CC(C)=CC=1)CC1=CC=C(C)C=C1 YFJBZOCDTYZZBH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 150000003003 phosphines Chemical class 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 22
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 6
- BMTDZORNBFQUEA-UHFFFAOYSA-K 2-ethylhexanoate;rhodium(3+) Chemical compound [Rh+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O BMTDZORNBFQUEA-UHFFFAOYSA-K 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003283 rhodium Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 150000003284 rhodium compounds Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940063013 borate ion Drugs 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- AMCCJKSQPYVMTD-UHFFFAOYSA-L 2-ethylhexanoate;rhodium(2+) Chemical compound [Rh+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O AMCCJKSQPYVMTD-UHFFFAOYSA-L 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- LVGLLYVYRZMJIN-UHFFFAOYSA-N carbon monoxide;rhodium Chemical compound [Rh].[Rh].[Rh].[Rh].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] LVGLLYVYRZMJIN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000005677 ethinylene group Chemical class [*:2]C#C[*:1] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- ITDJKCJYYAQMRO-UHFFFAOYSA-L rhodium(2+);diacetate Chemical compound [Rh+2].CC([O-])=O.CC([O-])=O ITDJKCJYYAQMRO-UHFFFAOYSA-L 0.000 description 1
- GYUYAVLQSFCVIT-UHFFFAOYSA-N rhodium;tribenzylphosphane Chemical compound [Rh].C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 GYUYAVLQSFCVIT-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- QRYINPBERILGBK-UHFFFAOYSA-N tris[(3-methoxyphenyl)methyl]phosphane Chemical compound COC1=CC=CC(CP(CC=2C=C(OC)C=CC=2)CC=2C=C(OC)C=CC=2)=C1 QRYINPBERILGBK-UHFFFAOYSA-N 0.000 description 1
- BULBMZQFEQRLPY-UHFFFAOYSA-N tris[(3-methylphenyl)methyl]phosphane Chemical compound CC1=CC=CC(CP(CC=2C=C(C)C=CC=2)CC=2C=C(C)C=CC=2)=C1 BULBMZQFEQRLPY-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
Definitions
- This invention relates to the rhodium catalyzed hydroformylation of olefins.
- Rhodium-based catalysts have the advantage, relative to cobalt-based catalysts, of being able to promote the hydroformylation of olefins under less severe operating conditions.
- Triaryl phosphines for example, are prone to conversion into alkyl diaryl phosphines under hydroformylation reaction conditions. These alkyl diaryl phosphines as rhodium ligands give lower activity catalysts compared to the triaryl phosphines.
- rhodium-based catalysts Another disadvantage of prior art rhodium-based catalysts is the fact that not all rhodium salts are suitable starting materials for the preparation of rhodium complexes. For example, it is frequently observed that a several hour induction period is required to transform the rhodium complexes into active hydroformylation catalysts. This problem is particularly acute when halide containing compounds of rhodium are employed for the preparation of rhodium complexes. Yet another disadvantage of rhodiums-based catalyst systems is the high cost of the rhodium metal employed for catalyst preparation. Where one employs low levels of rhodium metal in order to reduce catalyst costs, low reaction rates frequently result.
- An object of the present invention is a method for the rhodium-promoted hydroformylation of olefins to produce aldehydes in high yield and at a high rate of conversion.
- Another object of the present invention is a method for the rhodium-promoted hydroformylation of olefins to produce aldehydes in a highly selective reaction, i.e., with very low levels of by-product formation.
- Yet another object of the present invention is a rhodium complex catalyst which remains stable and soluble for extended periods of time under hydroformylation conditions.
- Still another object of the present invention is a method for the rhodium-promoted hydroformylation of olefins employing low levels of rhodium and low levels of ligand for the rhodium catalyst.
- a further object of the present invention is a method for the rhodium-promoted hydroformylation of olefins wherein the ratio of normal/branched chain aldehyde products can be varied within a wide range while retaining a high level of catalyst activity.
- R is Z; -SO 3 M, wherein K is H, an alkali metal or a quaternary ammonium moiety of the formula wherein each R v is independently a C 1 -C 20 alkyl, aryl, aralkyl or alkaryi moiety; and wherein x is a whole number which varies in the range of 0 up to 4 when Ar is phenyl, 0 up to 6 when Ar is naphthyl and 0 up to 8 when Ar is phenanthryl or anthracenyl.
- Exemplary compounds which satisfy this generic formula include: tribenzyl phosphine, tris(3,4-dichlorobenzyl)phosphine, tris(m-chlorobenzyl)phosphine, tris(p-chlorobenzyl)phosphine, tris(o-fluorobenzyl)phosphine, tris(m-fluorobenzyl)phosphine, tris(p-oethoxybenzyl)phosphine, tris(m-methoxybenzyl)phosphine, tris(m-methylbenzyl)phosphine, tris(p-methyIbenzyl)phosphine, tris(3,5-dimethylbenzyl)phosphine, tris([2,3]-benzobenzyl)phosphine, tris(o-oethyIbenzyl)phosphine, tris(p-tert-butylbenzyl)phosphine, tris(
- Preferred phosphines are those which have a C 3 axis of symmetry, i.e., symmetrical triorgano- substituted phosphines. Such materials are preferred because they are readily prepared and readily purified. Purified phosphine is highly desirable because such materials facilitate the preparation of high activity rhodium-based catalysts.
- phosphines contemplated for use in the practice of the present Invention are phosphines. which have a pKa within the range of about 3.5 up to 5.3 and a cone angle within the range of about 160 up to 195°.
- the pKa of phosphines is a measurement of the degree of reaction for the incomplete chemical reaction between the proton acceptor (phosphine) and a proton donor.
- the pKa is used as a measure of the relative basicities of the organophosphorus compounds.
- the term "pKa” is defined as the negative logarithm (to the base 10) of the equilibrium constant, Ka, for the proton acceptor-proton donor interaction referred to above.
- the monobasic borate ion, with the highest pKa value is the strongest base.
- the pKa values for numerous substituted phosphines have been measured and are reported by Streuli in Anal. Chem. 32, pp. 985-987 (1910).
- pKa values can be determined, such as for example, non-aqueous titrimetry in nitromethane solvent, tltration of solutions in mixed water methanol solvent systems, anhydrous acetic acid, acetic anhydride/toluene mixtures, acetic anhydride/dioxane mixtures, and the like.
- the cone angle is a measure of the steric properties of the phosphine. In general terms, the cone angle is the smallest angle of a cone (with its apex at a specified point in the phosphine moiety) which would contain all of the hydrocarbyl groups attached to the phosphorus atom.
- rhodium can be used as the rhodium component for preparation of the catalyst of the invention, provided that the source of rhodium employed can be converted into soluble carbonylligand complexes of rhodium.
- Suitable rhodium compounds include: rhodium (I) dicarbonyl acetonylacetonates, rhodium (II) 2-ethylhexanoate, rhodium (II) acetate, rhodium (0) carbonyls (e.g., Rh 6 (CO) 16 ,
- Rh 4 (CO) 12 Rh 4 (CO) 12 ), HRh(CO)(Ph 3 P) 3 , as well as mixtures of any two or more thereof. It is preferred that non-halogen containing rhodium compounds be used to avoid problems of low catalyst activity caused by the presence of residual halide, to avoid the corrosive effects of residual halide ions, and the like. In addition, salts of strong mineral acids are undesirable sources of rhodium because these compounds release acids which are detrimental to rhodium catalyst activity under hydroformylation conditions.
- rhodium 2-ethylhexanoate is a particularly preferred source of rhodium from which to prepare the complex catalyst of the invention because it is a convenient source of soluble rhodium, as it can be efficiently prepared from inorganic rhodium salts such as rhodium halides.
- the rhodium component can be added to the reactor , then the phosphine component ; or conversely, the phosphine component can be added to the reactor, then the rhodium component; or, alternatively, the preformed rhodium-phosphine complex can be eharged to the reactor.
- Suitable solvents include those which do not adversely affect the hydroformylation process and which are inert with respect to the catalyst, olefin, hydrogen and carbon monoxide feeds as well as the hydreformyletien ptoduets.
- Inert solvents of this nature are well known to those of skill in the art and include such solvents as benzene, xylene, toluene, as well as their substituted derivatives: pentanes, naphtha, kerosene, mineral oils, cyclohexane, cyclopentane, ethers, esters, etheresters, alcohols, acetals, ketones, water, as well as various mixtures thereof.
- Preferred solvents are those which are sufficiently high boiling to remain, for the most part, in a gas sparged reactor, and include such compounds as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TMPDMI; available from the Eastman Chemicals Division of Eastman Kodak Company as Texanol ® solvent), and its isomers, as well as the by-products of the hydroformylation reaction, such as alcohols, esters, acetals and hydroxyaldehydes which are retained as high boiling liquids at the bottom of subsequent distillation columns.
- TMPDMI 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
- the catalyst produces by employing the above-described starting materials and procedure is believes to consist primarily of compounds of the structure: wherein Ar is an aromatic ring having 6-14 carbon atoms, e.g., phenyl, naphthyl, phenanthryl and anthracenyl;
- each 2 is independently:
- M is H, an alkali metal or a quaternary ammonium moiety of the formula wherein each R v is independently a C 1 -C 20 alkyl, aryl, aralkyl or alkaryi moiety;
- x is a whole number which varies in the range of 0 up to 4 when Ar is phenyl, 0 up to 6 when Ar is naphthyl and 0 up to 8 when Ar is phenanthryl or anthracenyl;
- the process of the present invention can be carried out wi th widely var ied amounts of rhodium.
- amounts of catalyst containing as little as about 1 x 10 -6 moles of rhodium (calculated based on rhodium metal) per mole of olefin in the reactor zone can be employed.
- Such low catalyst concentrations are not generally commercially desirable since the reaction rates are frequently rather low.
- the molar ratios of phosphine to rhodium can vary over a wide range. Typically, the phosphine to rhodium ratio will vary within the range of about 2 up to 50. Preferably the molar ratio of phosphine to rhodium will vary within the range of 3 up to 30. In a most preferred embodiment, the molar ratio of phosphine to rhodium will vary within the range of about 6 up to 20.
- a particular advantage of the practice of the present invention is the fact that both catalyst activity and the ratio of normal to branched chain aldehyde products can be controlled by varying the phosphorus to rhodium ratio employed. For example, as higher ratios of phosphine to rhodium are employed, selectivity to the normal isomer (relative to the branched chain isomer) increases, while the reaction rate decreases.
- Olefins contemplated for use in the practice of the present invention include straight chain, branched chain, or cyclic, terminal or internal mono-oiefins containing in the range of 2 up to 20 carbon atoms and non-conjugated polyolefins typically having in the range of 5 up to 5,000 carbon atoms, e.g., polybutadiene, with each of the above optionally containing groups or substituents which do not interfere with the hydroformylation process.
- substituents which do not interfere with the hydroformylation process include:
- R'' is C 1 up to C 20 alkyl, aryl, alkaryi, aralkyl, or aeyl radical
- R''' is a C 1 up to C 20 alkyl aryl, alkaryi or aralkyl radical
- R' is independently selected from H, C 1 up to C 12 alkyl radicals or substituted alkyl radicals, and C 6 up to C 12 aryl radicals or substituted aryl radicals, and each R iv is independently selected from the members defined by R', where the R iv groups can be Joined together to form a eyclic acetal or ketal, - SR''; wherein R'' is as defined above, and
- R''' is as defined above.
- each R' is independently selected from H, C 1 up to C 12 alkyl or alkylene radicals or substituted alkyl or alkylene radicals, and C 6 up to C 12 aryl radicals or substituted aryl radicals; and x is a whole number between 1 and 20; compounds of the structure;
- R' is as defined above;
- R" is C. up to C 20 alkyl, aryl, alkaryl, aralkyl or acyl radical, and y is a whole number of 0 up to 20; esters of the structure:
- R' and x are as defined above; and R''' is C 1 up to C 20 alkyl, aryl, alkaryl or aralkyl radical; acetals and ketals of the structure:
- R' and y are as defined above; and each R is defined as in R', plus, the two R iv groups may be joined together to form a cyclic acetal or ketal sulfides of the structure;
- R', R ,, ', and y are as previously defined.
- alpha-olefins suitable for use in the practice of the present invention are ethylene, propylene, 1-butene, 2-methylpropylene, 2-methyl-1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
- 2-ethyl-1-hexene, 1-dodecene and 1-octedecene are also useful in the practice of the present invention.
- the internal olefins such as 2-butene and cyclic olefins such as cyclooctene.
- mixtures of olefins, particularly ethylene and propylene, can also be fed to the reactor.
- Preferred olefins employed in the practice of the present invention contain in the range of 2 up to 10 carbon atoms, with olefins containing in the range of 2 up to 4 carbon atoms being preferred.
- Suitable reaction vessels include gas sparged reactors, liquid overflow reactors, stirred tank reactors, trickle bed reactors, and the like, as are known to those of skill in the art.
- a presently preferred reactor for carrying out the process of the present invention with low boiling products is a gas sparged reactor such that the catalyst does not leave the reaction zone with the aldehyde product which is taken overhead by unreacted gases.
- a liquid overflow type of reactor may be more appropriate to facilitate product handling and recovery.
- the overhead gases are chilled in a vapor liquid separator to condense out the aldehyde product, with the gases being recycled to the reactor while the liquid product is let down to atmospheric pressure for separation and purification by conventional means.
- a side draw from the reactor can optionslly fee provided for sere complete product distinction.
- Small amounts of catalyst are withdrawn from the reactor along with the side draw of reaction medium.
- the catalyst can optionally be subjected to appropriate regeneration treatment before being returned to the reactor, following the addition of make-up ligand thereto.
- the process of the present invention is carried out et temperatures in the range of about 0 up to 190°C. Temperatures in the range of about 50 up to 150°C are preferred, with temperatures in the range of 75 up to 125°C being most preferred because reactions at such temperatures give excellent rate of reaction with minimum catalyst deactivation.
- Pressures in the range of about 15 up to 1500 psia are typically employed for the hydroformylation reaction.
- reaction pressure in the range of about 100 up to 450 psia are employed, with reaction pressures in the range of about 150 up to 250 psia being most preferred because economically attractive reactien rstes are obtained at these relatively low reaction pressures, which in turn reduces the cost of reaction equipment, the need for added compressor capacity, gas recycle, etc.
- Hydrogen to carbon monoxide ratios in the reaction zone can vary over a wide range. Typically, hydrogen to carbon monoxide ratios of about 0.5;1 up to 10:1 will be employed.
- Hydrogen to carbon monoxide ratios in the range of about 1:1 up to 6:1 are preferred, with ratios in the range of about 1.1:1 up to 5:1 being most preferred because high catalyst activity is obtained with minimum by-product formation when reaction is carried out at such ratios.
- reactant space velocities typically fall in the range of 1 up to 1000 standard cubic feed per minute per cubic foot of catalyst (SCFM).
- SCFM standard cubic feed per minute per cubic foot of catalyst
- reactant space velocities in the range of 25 up to 200 SCFM are employed, with reactant space velocities in the range of 50 up to 125 SCFM being most preferred because a t such space velocities, with relatively low molecular weight products such as butyraldehyde, a desirable balance is achieved between product production rate and fluid levels in the reaction vessel.
- the rate of reaction is limited by the level of reactant gas present in the reaction zone, while at higher gas flow rates, the reactor contents tend to be removed from the vessel faster than the rate of formation of additional product.
- the preferred gas flow rate with any given olefin feed will be a function of the total reactor pressure, reaction temperature, product production rate, and the like.
- the reagents employed for the invention hydroformylation process be substantially free of materials which may reduce catalyst activity or completely deactivate the catalyst.
- materials such materials as conjugated dienes, acetylenes, mercaptans, mineral acids, halogenated organic compounds, end free oxygen should generally be excluded from the reaction.
- no special precautions regarding the exclusion of water need be taken, as small amounts of water have not been found to be detrimental to the invention hydroformylation process.
- the reactor employed for the hydroformylation reaction described in the Examples consists of a vertically held stainless steel 4 foot by 1 inch (inside diameter) tube having a stainless steel filter element welded into its side near the bottom.
- the bottom of the tube has a drain valve and the top has a side port through which the vaporized products and unreacted gases leave the reactor.
- the top end of the tube is provided with a screwed plug which -can be removed for charging the catalyst and which contains a thermowell whereby the temperature of the catalyst solution (reaction medium) in the reactor is measured accurately.
- Hydrogen and carbon monoxide are fed to the reactor from cylinders via pressure regulators and flow controllers which use differential pressure cells and air actuated flow control valves to maintain precise flow.
- a third feed of nitrogen from a cylinder goes to the reactor via a pressure regulator and rotameter with needle valve.
- the carbon monoxide passes through a heated commercial "deoxo" unit as marketed by Engelhard Industries, Division, Engelhard Minerals and Chemicals Corp., Newark, N.J., to femove oxygen impurities.
- the nitrogen admixed with hydrogen is passed through a similar "deoxo" unit before entering the reactor.
- Propylene is fed as a liquid to a preheater section or plenum chamber, where it is combined with the other feed gases and is vaporized prior to entering the reactor via the stainless steel filter element.
- the propylene feed rate is measured using rate-of-level drop in a tank containing liquid propylene using an armored rotameter with a needle valve to control the liquid propylene feed rate.
- the catalyst is contained as a solution in the lower portion of the reactor tube and the reactant gases are sparged up through the solution as bubbles emanating from the filter element.
- Product butyraldehyde is formed in the catalyst solution where it accumulates and eventually is removed as a vapor by vapor/liquid equilibration with unreacted gases.
- This type of reactor is known as a vapor take-off or vapor stripped reactor.
- the hot gases are cooled upon leaving the reactor through said side port and the butyraldehyde product, along with some unreacted propylene, collects in a cooled high pressure separator connected by suitable conduit means to said side port.
- the noncondensed gases are let down to atmospheric pressure via a back pressure regulator which controls the reactor pressure.
- Additional butyraldehyde is condensed out of the atmospheric pressure gas stream by passing it through a series of three dry ice traps. Once an hour the contents of the high pressure separator and dry ice traps are collected and combined.
- the weight of butyraldehyde product obtained during the hour and its n/iso ratio are calculated using standard gas/liquid chromatographic techniques in combination with the crude weight of the product collected.
- a catalyst charge comprised of 0.044 gram of rhodium (as rhodium 2-ethylhexanoate) and 1.35 grams of tribenzylphosphine dissolved in 0.175 liter
- the reactor was operated continuously for 9 days under the conditions set forth above. After a line-out period of 48 hours during which the catalyst activity slowly and steadily increased, the catalyst produced aldehydes with a normal to branched isomer ratio of 1.65 to 1.69 at a production rate of 5.62 to 5.90 pounds of butyraldehyde per gram of rhodium per hour (lb. HB ⁇ /g-Rh-hr.). There was no detectable change in production rate or isomer distribution after the 48-hr. line-out period. At the end of the ninth day, an additional 2.90 grams of tribenzylphosphine was added to the catalyst.
- the normal to branched isomer ratio increased to 1.85 while the production rate declined to 3.23 to 3.51 (lb. HBu/g-Rh-hr.).
- the reaction was continued for an additional 3 days during which no further changes in isomer distribution or production rate were observed.
- the recovered catalyst was light yellow liquid, free of any solids.
- a catalyst charge comprised of 12 mg of rhodium (as rhodium 2-ethylhexanoate) and 1.24 grams of tribenzylphosphine dissolved in 0.175 liter of Texanol ® was charged to the reactor system described above. The reactor was maintained at 110°C and operated continuously for seven hours. The reaction was conducted in the same manner as set forth in Example 1, except that the H 2 /CO ratio was changed as noted in Table 1.
- a catalyst charge comprised of 31.25 mg of rhodium (as rhodium 2-ethylhexanoate) and 1.69 grams of tribenzylphosphine dissolved in 0.2 liter of Texanol ® solvent was charged to the reactor system described abovt.
- the reactor was maintained at a temperature in the range of about 100 up to 135°C, as noted in Table 2, and operated continuously for seven hours.
- the reaction was conducted according to the general procedure set forth above. Operating parameters and reaction results are set forth in Table 2.
- reaction temperature is an effective way to control the normal/iso product ratio.
- An increase in the normal/iso ratio of greater than 30% is observed with a variation in reaction temperature of less than 35°C.
- a catalyst charge comprised of 31.25 mg of rhodium (as rhodium 2-ethylhexanoate) and varying amounts of tribenzylphosphine (as noted in Table 3) dissolved in 0.2 liter of Texanol ® solvent was charged to the reaetor sygtem described above. Tht reactor was maintained et 125°C and operated continuously for seven hours. The reaction was conducted according to the general procedure set forth above. Operating parameters and reaction results are set forth in Table 3.
- a catalyst charge comprised of 15 mg of rhodium (as rhodium 2-ethylhexanoate) and varying amounts of tribenzylphosphine or tribenzylphosphine derivative (as noted in Table 4) dissolved in 0.2 liter of Texanol ® solvent was charged to the reactor system described above. The reactor was maintained at 125°C and operated continuously for seven hours. The reaction was conducted according to the general procedure set forth above. Operating parameters and reaction results are set forth in Table 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Hydroformylation d'oléfines à l'aide de catalyseurs complexes au rhodium. Les catalyseurs utilisés comprennent un complexe au rhodium ayant au moins une phosphine présentant une structure spécifique, par exemple tris(benzyl)phosphine. Des phosphines préférées ont un pKa compris entre 3,5 environ et 5,3 et un angle de cône de l'ordre de 160 à 195°. Des réactions d'hydroformylation à des températures et une pression relativement basses mais des vitesses de réaction élevées et une grande sélectivité au produit aldéhyde sont obtenues en appliquant la présente invention.Hydroformylation of olefins using complex rhodium catalysts. The catalysts used comprise a rhodium complex having at least one phosphine having a specific structure, for example tris (benzyl) phosphine. Preferred phosphines have a pKa of between about 3.5 and 5.3 and a cone angle of the order of 160 to 195 °. Hydroformylation reactions at relatively low temperatures and pressure but high reaction rates and high selectivity to the aldehyde product are obtained by applying the present invention.
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8333087A | 1987-08-10 | 1987-08-10 | |
US83330 | 1987-08-10 | ||
US07/225,103 US4871878A (en) | 1987-08-10 | 1988-07-27 | Low pressure rhodium catalyzed hydroformylation of olefins |
US225103 | 1988-07-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0379515A1 true EP0379515A1 (en) | 1990-08-01 |
EP0379515B1 EP0379515B1 (en) | 1993-10-20 |
Family
ID=26769178
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88908046A Expired - Lifetime EP0379515B1 (en) | 1987-08-10 | 1988-08-04 | Low pressure rhodium catalyzed hydroformylation of olefins |
Country Status (9)
Country | Link |
---|---|
US (1) | US4871878A (en) |
EP (1) | EP0379515B1 (en) |
JP (1) | JP2831011B2 (en) |
KR (1) | KR960004183B1 (en) |
CN (1) | CN1031835A (en) |
CA (1) | CA1305491C (en) |
DE (1) | DE3885103T2 (en) |
ES (1) | ES2007986A6 (en) |
WO (1) | WO1989001467A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3920423A1 (en) * | 1989-06-22 | 1991-01-03 | Basf Ag | METHOD FOR PRODUCING 2,3-DIALCOXYPROPANAL |
US5232989A (en) * | 1991-03-04 | 1993-08-03 | Monsanto Company | Functionalized polymers |
CN1035543C (en) * | 1993-01-09 | 1997-08-06 | 厦门大学 | Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine |
GB2274457A (en) * | 1993-01-25 | 1994-07-27 | Shell Int Research | Hydroformylation of unsaturated carbonyl compounds |
US5912364A (en) * | 1996-10-21 | 1999-06-15 | Eastman Chemical Company | Process for the preparation of 3-methyltetrahydrofuran |
US5840647A (en) * | 1997-09-15 | 1998-11-24 | Eastman Chemical Company | Hydroformylation process using novel phosphite-metal catalyst system |
US6130358A (en) | 1998-10-16 | 2000-10-10 | Eastman Chemical Company | Hydroformylation process using novel phosphite-metal catalyst system |
US6225509B1 (en) * | 2000-01-06 | 2001-05-01 | Arco Chemical Technology, L.P. | Allyl alcohol hydroformylation |
US6909019B1 (en) | 2004-05-25 | 2005-06-21 | Eastman Chemical Company | Process for preparing aldehydes |
US8492593B2 (en) | 2011-08-16 | 2013-07-23 | Eastman Chemical Company | Amido-fluorophosphite compounds and catalysts |
US9308527B2 (en) | 2014-03-17 | 2016-04-12 | Eastman Chemical Company | Phosphorous compounds useful as ligands and compositions and methods regarding them |
US12031091B2 (en) | 2019-05-24 | 2024-07-09 | Eastman Chemical Company | Recycle content cracked effluent |
WO2020242912A1 (en) | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
KR20220041177A (en) | 2019-07-29 | 2022-03-31 | 이스트만 케미칼 컴파니 | Process for making polyester with recycled monomers from pyrolysis and methanolysis |
US20220363862A1 (en) | 2019-07-29 | 2022-11-17 | Eastman Chemical Company | Recycle content cyclobutane diol polyester |
US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
WO2021092306A1 (en) | 2019-11-07 | 2021-05-14 | Eastman Chemical Company | Recycle content alpha olefins and fatty alcohols |
JP2021187800A (en) * | 2020-06-02 | 2021-12-13 | 三菱ケミカル株式会社 | Method for producing aldehyde |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0031590A1 (en) * | 1979-12-28 | 1981-07-08 | Union Carbide Corporation | Rhodium catalyzed hydroformylation process |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3527809A (en) * | 1967-08-03 | 1970-09-08 | Union Carbide Corp | Hydroformylation process |
DE2045169A1 (en) * | 1970-09-12 | 1972-03-23 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Treatment of oxo reaction mixts - by addn of aqs alkali hydroxide |
US4195042A (en) * | 1971-08-20 | 1980-03-25 | Phillips Petroleum Company | Rhodium hydroformylation catalyst |
DE2861830D1 (en) * | 1977-12-16 | 1982-07-01 | Monsanto Co | Hydroformylation of formaldehyde with rhodium catalyst |
US4593141A (en) * | 1979-02-12 | 1986-06-03 | Exxon Research And Engineering Co. | Hydroformylation catalysis by branched alkyl diaryl phosphine rhodium complexes |
JPS56125329A (en) * | 1980-03-07 | 1981-10-01 | Sagami Chem Res Center | Preparation of aldehyde having perfluoro group |
CA1166270A (en) * | 1981-04-30 | 1984-04-24 | Mitsuo Matsumoto | Method of producing 1,9-nonanedial and/or 9-hydroxy-7- nonen-1-al |
DE3234701A1 (en) * | 1982-09-18 | 1984-04-05 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING ALDEHYDES |
US4528403A (en) * | 1982-10-21 | 1985-07-09 | Mitsubishi Chemical Industries Ltd. | Hydroformylation process for preparation of aldehydes and alcohols |
DE3245883A1 (en) * | 1982-12-11 | 1984-06-14 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR HYDROFORMYLING OLEFINS |
US4533756A (en) * | 1983-11-07 | 1985-08-06 | Texaco Inc. | Process for synthesis of acrylic acid precursors via hydroformylation of vinyl ether |
DE3341035A1 (en) * | 1983-11-12 | 1985-05-23 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING ALDEHYDES |
DE3413427A1 (en) * | 1984-04-10 | 1985-10-17 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING ALDEHYDES |
DE3562618D1 (en) * | 1984-08-30 | 1988-06-16 | Ruhrchemie Ag | Process for making aldehydes |
US4578523A (en) * | 1985-05-29 | 1986-03-25 | Ruhrchemie Aktiengesellschaft | Process for the preparation of aldehydes |
DE3534314A1 (en) * | 1985-09-26 | 1987-04-02 | Ruhrchemie Ag | METHOD FOR PRODUCING ALDEHYDES |
US4755624A (en) * | 1987-02-18 | 1988-07-05 | Eastman Kodak Company | Low pressure hydroformylation process |
US4760194A (en) * | 1987-02-18 | 1988-07-26 | Eastman Kodak Company | Low pressure hydroformylation catalyst employing unique ligands and process using same |
US4742178A (en) * | 1986-11-10 | 1988-05-03 | Eastman Kodak Company | Low pressure hydroformylation of dienes |
-
1988
- 1988-07-27 US US07/225,103 patent/US4871878A/en not_active Expired - Lifetime
- 1988-08-04 JP JP63507110A patent/JP2831011B2/en not_active Expired - Lifetime
- 1988-08-04 WO PCT/US1988/002621 patent/WO1989001467A1/en active IP Right Grant
- 1988-08-04 DE DE3885103T patent/DE3885103T2/en not_active Expired - Lifetime
- 1988-08-04 KR KR1019890700609A patent/KR960004183B1/en not_active IP Right Cessation
- 1988-08-04 EP EP88908046A patent/EP0379515B1/en not_active Expired - Lifetime
- 1988-08-08 CA CA000574087A patent/CA1305491C/en not_active Expired - Lifetime
- 1988-08-09 ES ES8802493A patent/ES2007986A6/en not_active Expired
- 1988-08-10 CN CN88106529A patent/CN1031835A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0031590A1 (en) * | 1979-12-28 | 1981-07-08 | Union Carbide Corporation | Rhodium catalyzed hydroformylation process |
Non-Patent Citations (1)
Title |
---|
See also references of WO8901467A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR890701524A (en) | 1989-12-20 |
KR960004183B1 (en) | 1996-03-27 |
ES2007986A6 (en) | 1989-07-01 |
DE3885103D1 (en) | 1993-11-25 |
CA1305491C (en) | 1992-07-21 |
DE3885103T2 (en) | 1994-05-19 |
CN1031835A (en) | 1989-03-22 |
JP2831011B2 (en) | 1998-12-02 |
JPH03500770A (en) | 1991-02-21 |
WO1989001467A1 (en) | 1989-02-23 |
US4871878A (en) | 1989-10-03 |
EP0379515B1 (en) | 1993-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4871878A (en) | Low pressure rhodium catalyzed hydroformylation of olefins | |
EP0375573B1 (en) | Low pressure rhodium catalyzed hydroformylation of olefins | |
US4873213A (en) | Low pressure rhodium catalyzed hydroformylation of olefins | |
CA1191866A (en) | Hydroformylation process | |
EP0028378B1 (en) | Improved hydroformylation process using stable rhodium catalyst | |
US4400547A (en) | Hydroformylation process utilizing an unmodified rhodium catalyst and the stabilization and regeneration thereof | |
CA1191865A (en) | Hydroformylation process | |
EP0484977A2 (en) | Improved mixed aldehyde product separation | |
GB2193494A (en) | Hydroformylation process | |
CA1090823A (en) | Cyclic hydroformylation process | |
US4306087A (en) | Hydroformylation of olefinic compounds | |
WO1980001691A1 (en) | Process for the preparation of aldehydes | |
US4760194A (en) | Low pressure hydroformylation catalyst employing unique ligands and process using same | |
JPS5833209B2 (en) | Improved hydroformation method | |
KR20010023978A (en) | Hydroformylation process using novel phosphite-metal catalyst system | |
US4388476A (en) | Hydroformylation process with rhodium catalyst and oxygen stabilization thereof | |
CA1118451A (en) | Process for preparing aldehydes | |
CN107922450A (en) | The hydroformylation catalysts of halo phosphite ester containing isomer enrichment | |
CA1106407A (en) | Hydroformylation process | |
US4388477A (en) | Hydroformylation process employing unmodified rhodium-cobalt catalyst | |
US4587364A (en) | Hydroformylation process employing unmodified osmium-cobalt catalyst | |
US4474995A (en) | Hydroformylation process employing tetracarboxylatodiruthenium halide complex catalyst | |
KR810001464B1 (en) | Method of hydro formylation process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19900125 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT SE |
|
17Q | First examination report despatched |
Effective date: 19920414 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT SE |
|
REF | Corresponds to: |
Ref document number: 3885103 Country of ref document: DE Date of ref document: 19931125 |
|
ITF | It: translation for a ep patent filed | ||
ET | Fr: translation filed | ||
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: EASTMAN CHEMICAL COMPANY |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
EAL | Se: european patent in force in sweden |
Ref document number: 88908046.1 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070831 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070705 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20070802 Year of fee payment: 20 Ref country code: IT Payment date: 20070814 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070803 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20080803 |
|
EUG | Se: european patent has lapsed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20080803 |